New dibenzanthrone vat dye compounds



United States Patent NEW DlBENZAN'H-IRONE VAT DYE COB [POUNDS James M. Straley and Raymond C. Harris, Kingsport,

Tenn., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New .iersey No Drawing. Application March 25, 1954, Serial No. 418,781 6 Claims. (Cl. 260-353) This invention relates to new dibenzanthrone vat dye compounds, to new dibenzanthronyl compounds and to the processes for preparing the new compounds of the invention.

Dibenzanthrone (violanthrone) and various derivatives thereof are well known in the dyeing art. Although dibenzanthrone is still used extensively for the dyeing of cotton textile materials, it has a serious disadvantage in that it waterspots. That is, the shade of the dyeing varies with changes in humidity, the wet dyeing being considerably redder than relatively dry dyeings. Thus, if a cotton textile material dyed with dibenzanthrone should be partially wetted, the wet spots would appear redder than the dry spots. Many derivatives of dibenzanthrone also sufier from this fault. Caledon Jade Green (B2 2, B2 2-dirnethoxydibenzanthrone) and its derivatives are exceptions in this respect.

We have discovered that dibenzanthrone compounds containing a cyano group in the 16-position vat dye cotton textile materials clear, attractive blue shades, which do not waterspot, which are exceptionally fast to light and washing and which are intermediate in hue between the dyeings obtained with dibenzanthrone and the most widely used blue vat dye indanthrone. The new dibenzanthrone vat dye compounds are prepared by ring closing the new dibenzanthronyl compounds of our invention as fully described hereinafter.

The new dibenzanthronyl compounds of our invention are prepared by condensing a 9-methyleneanthrone compound which is unsubstituted in at least one of the land 8-positions with an unsaturated aliphatic cyano compound having the formula:

RCH=CH=CHCN wherein R represents a hydrogen atom, a methyl group or a cyano group to form the new Bz 2-cyano-Bz 1, B2 1- dibenzanthronyl compounds of our invention. The course of the reaction is believed to be as follows:

7 9 2 RCH=CHCH=CHCN Q-methyleneanthrone The various nuclei are numbered as indicated above.

The new dibenzanthrone vat dye compounds of our invention are prepared by ring closing the new B2 2- cyano-Bz 1, B2 l-dibenzanthronyl compounds of our invention. The course of the reaction is believed to be as follows:

R CN

Bz 2-eyano-Bz 2'-R-Bz 1, B2 1'-dibenzanthronyl 16-cyano-17-R-dibenzanthrone The dibenzanthrone nucleus is numbered as indicated above.

It is an object of our invention to provide new dibenzanthrone vat dye compounds. Another object of our invention is to provide new 132 2-cyano-Bz 1, B2 l'-dibenzanthronyl compounds. A further object is to provide satisfactory processes for the preparation of the new com-' pounds of our invention.

In preparing the new Bz Z-cyano-Bz 1, B2 1-dibenzanthronyl compounds of our invention a 9-methyleneanthrone compound which is unsubstituted in at least oneof the land 8-positions is condensed with an unsaturated aliphatic cyano compound having the formula:

RCH=CHCH=CHCN Wherein R represents a hydrogen atom, a methyl group or a cyano group. The condensation reaction is carried out in the presence of a solvent such as acetic acid, o-dichlorobenzene, 1,2,4-trichlorobenzene, tetrachloroethane or butyl Cellosolve, for example, in the presence of a mild oxidant such as air, oxygen, nitrobenzene, onitrotoluene, m-nitrotoluene or p-nitrotoluene, for example. When an oxidant such as nitrobenzene, o-nitrotoluene, m-nitrotoluene or p-nitrotoluene is employed, the oxidant serves both as an oxidant and a solvent and no other solvent or oxidant is needed. The condensation reaction is preferably carried out at a temperature of from about C. to about C. although somewhat higher and lower temperatures can be used. If desired, the reaction between the 9-methyleneanthrone compound and the unsaturated aliphatic cyano compound can be carried out prior to the oxidation step. However, it is preferred to carry out the condensation reaction in the presence of the oxidant.

9-methyleneanthrone compounds that can be employed include, for example, Q-methyleneanthrone, 9-methylene- 2-methylanthrone, 9-methylene-3-methylanthrone and 9- methylene-4-methylanthrone.

When a substituted 9-methyleneanthrone compound is used in preparing the new Bz 2-cyano-Bz 1, B2 1'-dibenzanthronyl compounds of our invention, a substituted dibenzanthronyl compound is obtained. Thus, the dibenzanthronyl compoundsof our invention may contain a 3 substituent such as a methyl group. When a single monosubstituted 9-methyleneanthrone compound is employed, the resulting dibenzanthronyl. compound will contain two like substituents, such as two methyl groups. When a mixture of an unsubstituted and a. monosubstituted 9- methyleneanthrone compound is employed, a dibenzanthronyl compound containing a single substituent is obtained. The substituents just referred to are in addition to the cyano group in the B2 2-position and any substituent present in the B2 2'-position.

The new Bz Z-cyano-Bz 1, Bz 1-dibenzanthronyl compounds of our'invention have the formula:

KAA/ V wherein X and Y eachrepresents a hydrogen atom or a methyl group.

As previously indicated, the new. lfi-cyanodibenzanthrone vat dye compounds of our invention are prepared by ring closing our new Bz Z-cyano-Bz 1, Bz 1'-dibenzan thronyl compounds. The ring closure is effected by caustic fusion using known techniques. 'We prefer to carry out ring-closure using alcoholic KOH at a temperature of from about 130 C. to'about 185 C., although somewhat higher and lower temperatures can be used. The

upper temperature limit of the caustic fusion reaction has not been determined by us but ring-closure below about 115 C. appears to be impractical.

The new dibenzanthrone compounds of our invention. have the. general formula:

dicted'that the cyano group would remain intact, analysis shows that the cyano group is present in the 'dibenzanthrone compoundsof our invention.

The following. examples illustratethe compounds of. our invention and the manner in which they are prepared.

Parts are expressedby weight! Example 1 To a solution of 20 partsof 9-methyleneanthrone in- 40 parts of nitrobenzene there was added, with stirring, below the surfaceof the liquid at 150 C. 4 parts-of lcyanobutadiene-1,3 over a period of about-15 minutes. The temperature of the reaction mixture was raised.to

methyl alcohol were, added thereto.

4. bright yellow, microcrystalline powder which imparts a bright red color to concentrated sulfuric acid and does'not melt below 360 C.

Example 2 To a solution of 20 partsof 9-methyleneanthrone in 40 parts of nitrobenzene there was added, with stirring, below the surface of the liquid at 130 C; 4 parts of 1-cyanobutadiene1,3 over a period of about minutes. The reaction mixture was held at 130 C.-135 C. for 1 hour after which it was raised to 180 C.185 C. and

held at this temperature for 2 hours. The reaction mixture was then cooled to below 100 C. and 25 parts of After chilling to 10 C. the reaction mixture was-filtered to recover'the precipitated'product and the-productrecovered on the filter 'waswashed well with methyl alcohol andthen dried at 110 C. Using this procedure 10 to 18 partsof-- a product identical with that of- Example 1- was obtained.

, Example 3 10 parts of 9..-m ethyleneanthrone were: added,jwith-= stir1ing, at;100 C. to. 2 8. partsof 1,2,4-trichlorobenzene.

: to;170. C. anda stream; of air was passed through the 180 C9185 C. and held at this temperature for two} l hours; The reaction mixture was then cooled to" below 100 C. and 25 parts of methyl alcohol were added there to following which the reaction mixture was chilled tofi 10-C. The product which 'precipitated'w'as recovered by :filtration, washed well with'dnethyl alcohol and then 7 driedfat-.110'C. The yield was 8 to 15'parts of-Bz- 21cya'no-Bz 1,- Bzl-l -dibenzanthronyl. The product is a 3 parts of 'sorbon trile (CH3CH=CHC H=ICHCN). were.

added andthe temperature of. the resulting; reaction mix:

ture was held at- C. for two hourswhile stirring. Theternperature ,of the reaction mixture, was then raised reaction mixture for 2.5 rhoursat this temperature. 7 The reaction mixture was thencooledgto room temperature,

filtered, and the product which collected on. the filter was washed well with methyl alcohol and then driedat dibenzanthronyl was obtained as a-bright yellow powder melting at 245 0- 247." Grand soluble in concentrated sulfuric acid to-a bright, fluorescent red solution.

Example 4 10 parts'of 9-methyleneanthrone were dissolved in 20' parts of butyl Cellosolve at 100 C; and 3 parts ofsorbonitrile were added thereto withstirring. The temperature of the-reaction mixture wasraised to C. andthen 2 parts of nitrobenzene were added. The temperature of the reaction mixture was held at 175 C.-180' C. for one hour while stirring, after which the reaction rm'xture was allowed to cool overnight. .The product formed was recovered by filtration, washed'well with ethyl alcohol anddried. The product obtained is-identical withthat of Example 3,- V

Example 5 A solution of 52 parts of 1,4-dicyanobutadiene-1,3 and 206 parts of 9-methyleneanthrone Was prepared in 400 parts of 1,2,4-trichlorobenzene at 100 C. The',r'esulting solution was held at 100 C.-105 C. for 1.5 hours. 70.

parts of nitrobenzene were added and thereaction mix ture resulting was heated at 150 C. for 1 hour. Following this the temperature of the reaction mixture was raised to 180 C. C. maintained at this temperature for 10 minutes and then allowed to cool to 90 C. 500

parts of methyl alcohol were added to the reaction mix-' ture, following which the reaction mixture was cooled to 10 C. and filtered. The product recovered on the filter was washed free of 1,2,4-trichlorobenzene with methyl alcohol and then dried at 110 C. 40 to 70 parts of Bz 2, Bz,2.'-dicyano-Bz-1,'Bz 1-dibenzanthronyl were thus obtained as a bright yellow powder melting at 328 C.- 329 C. and soluble in concentrated sulfuric acid to a bright orange fluorescent solution.

Example 6 Bythe. use of 21.2 parts of 9-methylene-4-methylanthrone in place of Q-methyleneanthrone in Example 1 a...

Bz 2-cyano-Bz 1, B2 1'-di'benzanthronyl compound having two methyl groups (one methyl group on each benzanthronyl nucleus) is obtained.

Example 7 By the use of 21.2 parts of 9-methylene-2-methylanthrone and 9-methylene-3-methylanthrone, respectively, in place of 9-methyleneanthrone in Example 1, B2 2- cyano-Bz 1, Bz 1'-dibenzanthronyl compounds having two methyl groups (one methyl group on each benzanthronyl nucleus) are obtained.

Example 8 A smooth melt was prepared from parts of potassium hydroxide and 16 parts of ethyl alcohol at 120 C. 1 part of the reaction product of Example 1 was added and the temperature of the reaction mixture was raised to 135 C. over a period of one hour. The reaction mixture was stirred at 135 C.145 C. for 2 hours and then drowned in water. The resulting solution was blown out with air at 95 C. to oxidize the dye product formed and to cause it to precipitate. The precipitated reaction product was recovered by filtration, washed well with hot water and dried at 110 C. 0.9 part of 16- cyanodibenzanthrone was obtained as a dark blue powder. The reaction product is soluble in concentrated sulfuric acid with a deep violet color and dyes cotton in beautiful navy blue shades from a violet vat. The presence of the unchanged nitrile group was confirmed by chemical analysis for nitrogen and by infrared spectroscopy.

Example 9 A smooth melt was prepared from 20 parts of potassium hydroxide and 40 parts of isobutyl alcohol at 110 C.120 C. 2 parts of the reaction product of Example 3 were added and the temperature of the reaction mixture was raised to 140 C. over a period of one hour. The reaction mixture was stirred at 145 C.-155 C. for 2.5 hours and then poured into 500 parts of hot water. The resulting solution was blown out with air at the boil to oxidize the dye product formed and to cause it to precipitate while removing the isobutyl alcohol by steam distillation at the same time. The reaction product was recovered by filtration, washed well with hot water and then dried at 110 C. 1.6 parts of 17-methyl-16-cyanodi benzanthrone were obtained as a blue powder. The reaction product dissolves in concentrated sulfuric acid with a deep violet color and dyes cotton navy blue shades which are somewhat greener and duller than the product of Example 8 from a dull violet vat. The presence of the unchanged nitrile group was confirmed by analysis for nitrogen and by infrared spectroscopy.

Example 10 A melt was prepared at 120 C. from 45 parts of potassium hydroxide and 80 parts of ethyl alcohol. 9 parts of the reaction product of Example 5 were added and the reaction mixture resulting was brought to a temperature of 150 C. over a period of one hour. The reaction mixture was then stirred at 155 C.165 C. for 2 hours after which it was drowned in water. The solution resulting was blown out with air at 95 C. to oxidize the dye product formed and to cause it to precipitate. The precipitated reaction product was recovered by filtration, washed well with hot water and then dried at 110 C. 7.6 parts of 16,17-dicyanodibenzanthrone were obtained as an almost black powder soluble in sulfuric acid to a deep blue-violet color. The reaction product dyes cotton gray-blue shades from a brown-violet vat.

Example 11 By the use of 9 parts of the reaction product of Example 6 (a dimethyl-Bz 2-cyano-Bz 1, B2 1'-dibenzanthronyl compound) in Example 10 in place of the re- 6 action product of Example 5 (B2 2, B2 2-dicyano-Bz 1, B2 1'-dibenzanthronyl) a dimethy1-16-cyanodibenzanthrone compound is obtained. The reaction product dyes cotton blue.

Example 12 By the respective use of 9 parts of the reaction products of Example 7 in Example 10 in place of the reaction product of Example 5, dimethyl-16-cyanodibenzauthrone compounds are obtained which dye cotton blue.

Dyeing with the vat dye compounds of the invention is performed according to the usual strong-alkali vat procedure. Dyeing can be carried out as follows:

0.05 gram of dyestufl are well ground with a few drops of Monopol oil (sulfonated castor oil) and rinsed into a dye-bath. The dye-bath is brought to a total volume of cc., using soft water, and 0.5-1 gram of NaOH and 075-1 gram of sodium hydrosulfite are added. The temperature of the dye-bath is raised to 50 C. and 5 grams of a well wet-out cotton goods are entered and dyed at 50 C.55 C. for 1 hour. The dyed cloth is removed, rinsed and hung in air until oxidation is complete. The dyeings are finished by a 20 minute boil in a 0.5% aqueous sodium carbonate solution, rinsing with water and drying.

While the manner in which our new vat dye compounds are applied to cotton, for example, constitutes no part of our invention, it will be understood that the dyeing procedure given above is merely illustrative and not limitative of the manner in which they may be applied to cotton goods.

While methyleneanthrone and a number of substituted methyleneanthrone compounds are known compounds, it is here noted that methyleneanthrone can be prepared as described by K. H. Meyer, Liebigs Annalen, vol. 420, page (1920). Substituted methyleneanthrone compounds can be prepared by the method just referred to for the preparation of methyleneanthrone by the use of a substituted anthrone compound in place of anthrone.

We claim:

1. The dibeuzanthrone compounds having the general formula:

wherein X and Y each represents a member selected from the group consisting of a hydrogen atom and a methyl group.

3. The dibenzanthrone compounds having the general formula:

I -C Y 7 8 wherein-R represents a member-selecitedironf' the group: 7 References Cibed insthe file of this patent COHSiSfiI l g Of: 3 hydrogen atom,& methyLgroup and 21 UNITED ATENTS cyanm groupi and X and..Y each represents'the same I t 7 member selected from the group consisting'ofi aihydro 1 840O Hertz "5 1941 gen atom and a methyl group. 5 2,619,492 iRatndall 17952 4 lfi.cyanodib enzanthron el 'a y --1 y 5-.- 17-methyl-1Geyanodibenzanthrone.

2,645,646 Randall July '14, 1953 6.16,l7 dicyanodibenzanthrone. j t V 

1. THE DIBENZANTHRONE COMPOUNDS HAVING THE GENERAL FORMULA: 